Niobium and tantalum octahedral Halides: Vibrational properties and Intra–Cluster interactions

Shamshurin, Maxim V.; Martynova, S. A.; Sokolov, Maxim N.; Benassi, Enrico

doi:10.1016/j.poly.2022.116107

Cited by 3 publications

(7 citation statements)

References 84 publications

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“…The bridging halogen atoms are characterized by a homogenous region of non-null values of ELF, which gets thinner and decreases along the direction toward the center of the cluster and broadens on the external space; the maximum decreases in the order Cl > Br (> I). Compared to the maps computed for homohalides, the values of ELF are higher and their spatial gradient more eccentric; this finding is in agreement with the increase of negative charge attributed to the halogen atoms due to the presence of CN groups with respect to X a . The ELF about the apical cyanides is characterized by the presence of the three regions of azimuthal symmetry of high values, viz.…”

Section: Resultssupporting

confidence: 80%

“…The symmetry of the highest-occupied MOs (HOMO; Figure S7) and HOMO-1 of all halocyanide clusters coincides with that of the corresponding MOs of the homohalides ( a 2u and t 1u , respectively, independent on metal or halide). For all compounds, the isosurface of HOMO shows zero density on the CN groups.…”

Section: Resultssupporting

confidence: 53%

“…The topological properties computed at the Bader theory level and the results obtained upon NBO analysis indicate a qualitatively similar topology for halocyanide clusters and homohalide clusters . The maps of the electron localization function (ELF; Figure ) show high values about metal centers; around the nucleus, there are axial lobes (maxima), separated by hollows with lower ELF values.…”

Section: Resultsmentioning

confidence: 54%

“…, B3LYP/Def2TZVPP. This level of theory had also been found to give excellent results for the corresponding halide clusters, [M 6 X 12 X 6 ] 4– …”

Section: Resultsmentioning

confidence: 93%

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Niobium and Tantalum Halocyanide Clusters: The Complete Family

et al. 2022

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Synthetic procedures providing straightforward access to the whole family of Nb and Ta halide clusters with terminal cyanide ligands have been developed. Corresponding [M 6 X 12 (CN) 12 ] 4− (M = Nb, Ta; X = Cl, Br) can be accessed by ligand-exchange procedures from K 4 Nb 6 X 18 (X = Cl, Br) and Bu 4 NCN, (Et 4 N) 2 [Ta 6 Cl 1 8 ] and Bu 4 NCN and from [Ta 6 Br 12 (H 2 O) 4 Br 2 ]•4H 2 O and KCN in moderate to high yields (50−80%). The products were isolated as Bu 4 N salts. The compounds were investigated both experimentally and by quantum chemistry, revealing correlations between structural, electrochemical, electrostatic, electronic, and topological features as a function of type of metal, halide, and charge.

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Section: Resultssupporting

confidence: 80%

Section: Resultssupporting

confidence: 53%

Section: Resultsmentioning

confidence: 54%

“…, B3LYP/Def2TZVPP. This level of theory had also been found to give excellent results for the corresponding halide clusters, [M 6 X 12 X 6 ] 4– …”

Section: Resultsmentioning

confidence: 93%

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Niobium and Tantalum Halocyanide Clusters: The Complete Family

et al. 2022

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“…Apart from the signal at 1627 cm −1 assigned to the bending vibration of water molecules, the spectrum of the pure tantalum cluster material does not show additional signals in the range of 500–2700 cm −1 . Note that the characteristic {Ta 6 Br i 12 } 2+ cluster core IR vibration bands at lower frequencies are not detectable within the registered spectral window [ 45 ].…”

Section: Resultsmentioning

confidence: 99%

Nanostructured Hybrids Based on Tantalum Bromide Octahedral Clusters and Graphene Oxide for Photocatalytic Hydrogen Evolution

et al. 2022

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The generation of hydrogen (H2) using sunlight has become an essential energy alternative for decarbonization. The need for functional nanohybrid materials based on photo- and electroactive materials and accessible raw materials is high in the field of solar fuels. To reach this goal, single-step synthesis of {Ta6Bri12}@GO (GO = graphene oxide) nanohybrids was developed by immobilization of [{Ta6Bri12}Bra2(H2O)a4]·4H2O (i = inner and a = apical positions of the Ta6 octahedron) on GO nanosheets by taking the advantage of the easy ligand exchange of the apical cluster ligands with the oxygen functionalities of GO. The nanohybrids were characterized by spectroscopic, analytical, and morphological techniques. The hybrid formation enhances the yield of photocatalytic H2 from water with respect to their precursors and this is without the presence of precious metals. This enhancement is attributed to the optimal cluster loading onto the GO support and the crucial role of GO in the electron transfer from Ta6 clusters into GO sheets, thus suppressing the charge recombination. In view of the simplicity and versatility of the designed photocatalytic system, octahedral tantalum clusters are promising candidates to develop new and environmentally friendly photocatalysts for H2 evolution.

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